Azo, nitro, anthraquinone, and phthalocyanine dyestuffs having a triazine or pyrimidine ring carrying a thioacylamide substituent



United States Patent M A20, NlllRi), ANTI-HRAQUENGNE, AND PHTHALQ- CYANHNE DYESTUFFS HAVENQ A TRIAZHNE GR PYRIiMdDlNE litlNG (IARi YKNG A THIG- ACYLAMEDE. UETHUENT George de Winter Anderson, Peter Albert Mack, and Frederick Andrew Waite, all of Manchester, England, assignors to imperial Qlrernical industries Limited, London, England, a corporation of Great Britain No Drawing. Filed June 2% 1964), Ser. No. 39,722

Qlainrs priority, application Great Britain Dec. 31, W59

1 (Ilaim. (Ell. 269-146) This invention relates to new dyestuffs and more particularly it relates to new dyestuffs which are valuable for colouring natural and artificial textile materials.

According to the invention there are provided the new dyestuffs which contain at least one group of the formula:

wherein R represents a hydrogen atom or a substituted or unsubstituted alkyl radical or a cycloalkyl radical, Z represents a 1:3:5-triazine or pyrimidine ring which is attached to the nitrogen atom N through a carbon atom of the said ring and which carries at least one group of the formula:

Formula II each of which is attached to a carbon atom of the 1:3:5- triazine or pyrimidine ring, wherein R and R represent hydrogen atoms or substituted or unsubstituted hydrocarbon radicals and may be the same or different.

Each of the groups of Formula I, as hereinbefore defined, is attached to a carbon atom present in the dyestutl. The said carbon atom may form part of an aryl residue present in the dyestutt or may form part of an alltyl chain which is directly attached to an aryl residue present in the dyestuii or is attached through a bridging atom or group. The dyestuli may be a member of any known dyestufl series and preferably it is a dyestufi' of the 2.20, which may be monoazo or polyazo, nitro, anthraquinone or phthalocyanine series, and which may or may not contain at least one water-solubilising group such as allrylsulphone, a carboxylic acid or a sulphamyl group and pr ferably a sulphonic acid group. If desired the dyestuii may also contain coordinately bound metal such as coordinately bound copper, chromium or cobalt.

As examples of the substituted or unsubstituted hydrocarbon radicals represented by R and R there may be mentioned alltyl radicals for example lower alkyl radicals such as methyl, ethyl, propyl and butyl, substituted alkyl radicals for example substituted lower alkyl radicals such as hydroxy lower allryl radicals for example fi-hydroxyethyl and [3:y-dihydroxypropyl, alkoxy lower alkyl radicals such as B-ethoxyethyl and fl-rnethoxyethyl and aryl lower alkyl radicals such as benzyl and ,B-phenylethyl, cycloalltyl radicals such as cyclohexyl, aryl radicals for example niouocyclic a-ryl radicals such as phenyl, tolyl, chlorophenyl and methoxyphenyl and dicyclic aryl radicals such as naphthyl.

When the 1:3 :S-triazine ring represented by Z contains only one group of Formula It then the 1:3:5-triazine ring Z may carry an additional substituent, or when the pyrimidine ring represented by Z contains less than 3 groups of Formula II then the pyrimidine ring may carry an additional substituent or substituents. As examples of such substituents which are attached to a carbon atom or atoms of the said rings there may be mentioned halogen atoms such as chlorine and bromine, mercapto, substituted men capto groups such as met-hylrnercapto, carboxymethyl- Patented Bee. 3, 19-33 mercapto and phenylrnercapto, alkyl radicals such as methyl and ethyl, aryl radicals such as phenyl and tolyl, hydroxy, alkoxy radicals such as methoxy, ethoxy, propoxy and butoxy, :aryloxy radicals such as phenoxy, sulphophenoxy and chlorophenoxy, amino groups, substituted amino groups such as methylamino, ethylamino, ,B-hydroxyethylalmino, dimethylarnino, diet-hylarnino, di-(flhydroxyethyl)amino, aniline, sulphoanilino, disulphoaniline, carboxyanilino and sulphonaphthylamino, dilkyldithiocarbarnyl radicals such as diethyldithiocarbarnyl and N-methyl-N-ethyldithiocarbarnyl, n-itro, cyano, thiocyano and sulphonic acid groups.

The substituted or unsubstituted alkyl radicals represented by R are preferably lower alkyl radicals such as rethyl, ethyl, propyl, and butyl which may contain substituents such as hydroxy or mcthoxy groups. As an example Of a cycloalkyl radical represented by R there may be mentioned the cyclohexyl radical.

According to a further feature of the invention there is provided a process for the manufacture of the new dyestuffs, as erein before defined, which comprises reacting a dystutl compound containing at least one group of the formula:

l R Formula III wherein R has the meaning stated above and Z represents a 1:3 z5-triazine or pyrimidine ring which is attached to the nitrogen atom N through a carbon atom of the said wherein R and R have the meanings stated above and W represents a hydrogen or a metal atom.

As examples of the metal atoms represented by W there may be mentioned alkali metal atoms such as sodium and potassium.

As examples of the halogen atom or atoms which are attached to the 1:3:5-triazine or pyrimidine ring there may be mentioned bromine and above all chlorine atoms.

This process of the invention may be conveniently brought about by adding an aqueous solution or suspension of the compound or" Formula IV to a solution or suspension of the dyestun compound containing at least one group of the Formula H1 in Water or in a water-miscible organic liquid, for example ethanol or acetone, or in a mixture of water and a water-miscible organic liquid, stirring the mixture so obtained, preferably at a temperature between 10 and (3., if necessary adding sodium, carbonate to maintain the pH of the rnixture between 5 and 1G, and filtering olt the dyestufi which is precipitated. if desired sodium chloride :and/ or water can be added to ensure complete precipitation of all the dyestuil.

When the 1:3:5-triazine or pyrimidine rep-resented by Z carries more than one halogen atom then it is possible by suitable choice of the reaction conditions to replace more than one of the said halogen atoms by groups of Formula II. In general it is found that the use of an excess of the compound of Formula IV and an increase in the reaction temperature results in replacement of user\. than one of the halogen atoms by the groups of Formula l1.

As specific examples of the compounds of Formula IV which may be used in this process of the invention there may be mentioned thioacetamide, thioacetanilide, thiopropionamide, N-ethyl thioacetarnide, N-ethylthiopropionamide, N-iso-butylthiopropionarnide, N-iso-arnyl thioacetamide, ethoxy thioacetarnide, thiobenzarnide, phenyl thicace-tamide, Z-methyl thiobenzarnide; N-ethyl thiobenzamide, N-methyl phenylthioacetamide, thioacet-p-toluidide, thioacetbenzylamide, thio-a-naphthamide, thio-B- naphthamide, 4-chlorothioacetanilide, 4-nitrothioacetanilide and 4-chlorothiopropionanilide.

The dyestuff compounds containing at least one group of Formula III which are used in this process of the invention may themselves be obtained by reacting a dyestuif compound containing at least one NHR group with a 1:3 :S-triazine or pyrimidine containing at least 2 halogen atoms.

As example of l:3:5--triazines or pyrimidines containing at least 2 halogen atoms which can be used to obtain the dyestuff compounds containing at least one halogen atom used in the process of the invention there may be mentioned cyanuric chloride, cyanuric bromide, 2:4-dichloro-l :3 :S-triazine, 2-methoXy-4 6-dichloro-l :3 :S-triazine, 2-ethoXy-4:6-dichloro-1 :3 S-triazine, 2amethyl-4: 6- dibromo-l 3 :S-triazine, 2-phen-yl-4 6-dichloro-l 3 :S-triazine, 2-methylamino-4 6-dichloro-l 3 S-triazine, 2-ethylamino-4:6-dichloro 1:3 :5 triazine, 2 phenoxy 4:6-dichloro-l:3:5-triazine, Z-(sulphophenoxy) 4:6 dichloro- 1 :3 S-tn'azine, 2-amino-4:-6-diohloro-l :3 5-triazine, 2-anilino-4:6-dichloro-l:3:S-triazine, 2-(2-, 3'- or 4'-sulphoanilino)-4:6 dichloro 1:3:5 triazine, 2-(3':5-disulphoanilino)-4:6-dichloro-1:3:5-triazine, 2-(2-, 3'- or 4'-carboxyani1ino)-4: 6 dichloro 1:3:5 tri azine, Z-mercapto- 4:6-dichloro-l :3 :5 triazine, 2 hydroxy 4:6 dichloro- 1 :3 :S-triazine, 2-methyl-mercapto-4 6-dichloro-l :3 S-triazine, 2-phenylmercapto-4: 6-dibromo-l 3 5-triazine, 2 :4: 6- trichloropyrimidine, 2: 4: 6-tribromopyrimidine, 2: 4:5 6- tetrachloropyrimidine, 2 z 4 5 6-tetrabromopyrimidi-ne, 2:4:6-trichloro-S-nitropyrimidine, 2:4-dichloro-5-nitro-6- methylpyrimidine, 2 4-dichloro-S-nitropyrimidine, 2:4: 6- trichloro-S-cyanopyrimidine, 5-cyano 2 methyl 4:6-dichloropyrimidine and 2-methyl-4:6-dichloro-5-nitropyrimidine.

Each of the -NHR groups present in the dyestuff compound is directly attached to a carbon atomor an aryl residue present in the dyestuif compound or each of the --NI-IR groups is attached to a carbon atom which forms part of an alkyl radical which is directly attached to an aryl residue present in the dyestuff compound or is attached through a linking atom or group. As examples of such linking atoms or groups there may be mentioned As examples of dyes-tuft compounds containing at least one NHR group, as hereinbefore defined, which may be used to obtain the dyestuif compounds containing at wherein D represents an at most di-cyclic aryl radical which is free from azo groups and NHR groups, the NHR group is preferably attached to the 6-, 7- or 8-position of the naphthalene nucleus, and which may contain a sulphonic acid group in the 5- or 6-position of the naphthalene nucleus.

D may represent a radical of the naphthalene or benzene series which is free from azo subs-tituents, for example a stilbene, d'phenyl, ibenzthiazolylphenyl or diphenylamine radical. Also in this class are to be considered the related dyestuffs in which the NHR group, instead of being attached to the naphthalene nucleus, is attached to a benzoylamino or anilino group which is 4 attached to the 6-, 7- or 8-position of the naphthalene nucleus.

Particularly valuable dyestuffs are obtained from those wherein D represents a sulphonated phenyl or naphthyl radical, especially those which contain a SO H group in ortho position to the azo link; the phenyl radical may be further substituted for example, by halogen atoms such as chlorine, alkyl radicals such as methyl, acylamino groups such as acetyl-amino and alkoXy radicals such as methoxy.

(2) Disazo compounds of Formula V, wherein D stands for a radical of the azobenzene, azonarphthalene or phenylazonaphthalene series and the naphthalene nucleus is substituted by the NHR group, and optionally by sulphonic acid as in class 1.

(3) Monoazo compounds of the formula:

wherein D stands for an at most dicyclic aryl radical as described for class 1 and is preferably a disulphonaphthyl or a stilbene radical, and the benzene nucleus may contain further substituents such as halogen atoms, or alkyl, alkoxy, carboxylic acid and acylamino groups.

(4) Monoor disazo compounds of the formula:

HlTTD --N=NK wherein D represents an arylene radical such as a radical of the azobenzene, azonaphthalene or phenylazoniaphthalene series, or, preferably, an at most dicyclic arylene radical of the benzene or naphthalene series, and K represents the radical of a naphthol su-lphonic acid or the radical of an enolised or enolisa-ble ketomethylene compound (such as an acetoacetarylide or a S-pyrazolone) having the OH group 0- to the azo group. D, preferably represents a radical of the benzene series containing a sulphonic acid group.

(5) Monoor disazo compounds of the formula:

wherein D represents a radical of the types defined for D in classes 1 and 2 above and K represents the radical of an enolisable ketome-thylene compound (such as an acetoacetarylide or a 5'-pyrazolone) having the OH group in a-position to the az'o group.

(6) The metal complex, e.g. the copper, chromium and cobalt complex, compounds of those dyes of Formulae V, VI and VII (wherein D K and K have all the respective meanings stated) which contain a metallisable (for example, a hydroxyl, lower alkoxy or carboxylic acid) group ortho to the azo group in D (7) Anthraquinone compounds of the formula:

0 Irma H o sour wherein Pc represents the phthalocyanine nucleus prefel ably of copper phthalocyanine, w represents ()H and/or" -NH Y represents a bridging group"; preferably an-ali-' 7 methyl 4 (4" nitro 2" carboxyphenylazo) pyrazolone.

In class 7:

1-amino-4-( 3 -amino-4-sulphoanilino) anthraquinon -2- sulphonic acid, 1-amino-4- (4'-amino-3 -sulphoanilino) anthraquinone-- 2 S-disulphonic acid, 1-amino-4- [4' 4-am=ino-3 "-sulphophenyl) anilino] anthnaquinone-Z 5-disulphonic acid, 1-amino-4[4-(4"-amino-2"-sulphophenylazohnilino} :anthraquinone-Z S-disulphonic acid, 1-amino-4-(4-methylamino-3 -sulphoanilino) anthraquinone-Z-sulphonic acid.

In class 8:

3-(3'-amino-4'-sulphophenyl)sulphamyl copper ph thalocyanine-tri-3-sulphonic acid,

Di-4-(3aamino-4'-sulphophenyl)sulphamyl copper phtha-- locyanine-di-4-sulphonic acid,

3-( 3 -aminophenylsulphamyl) -3-sulphamyl-copper phthalocyanine-di-3-sulphonic acid,

In class 9: 4-amino-2-nitro-diphenylamine-3,4'-disul-- phonic acid.

Specific examples of dyestuff compounds containing at. least one group of Formula III which can be used in thisv process of the invention are described in British specifi-- cations Nos. 209,723, 298,494, 467,815, 503,609, 772,030,. 774,925, 775,308, 780,591, 781,930, 784,221, 785,120,, 785,222, 802,935, 803,473, 805,565, 822,047, 822,948,. 825,377, 826,405, 828,353, 829,042, 832,400, 833,396,v 834,304, 836,248, 836,647, 837,035, 837,124, 837,953,. 837,985 and 837,990 and in Belgian specifications Nos. 556,092, 558,801, 558,816, 558,817, 558,884, 558,957, 559,782, 559,945, 560,791, 560,792, 560,793, 560,794, 560,795, 563,439, 563,862, 569,115, 570,122, 570,343, 571,238, 571,523, 571,893, 571,942, 572,833, 572,967, 573,299, 573,300, 578,742, 578,932 and 581,401, and in United States Patent No. 2,258,977.

According to a further feature of the invention there is provided a modified process for the manufacture of the new dyestuffs which are azo dyestuffs containing at least one group of Formula I which comprises diazotising a primary amine or the corresponding sulphamic acid and coupling the diazo compound so obtained with a coupling component, the primary amine and/ or the coupling component containing at least one group of Formula I.

This modified process of the invention may be conveniently brought about by adding sodium nitrite to a solution or suspension of the primary amine, which can be an aminoazo compound (or the corresponding sulphamic acid), in a dilute aqueous solution of hydrochloric acid and adding the so obtained solution or suspension of the diazo compound to a solution of the coupling component and filtering off the azo dyestuff which is precipitated. if desired sodium chloride can be added to ensure complete precipitation of all the azo dyestufi.

The primary amine, or the corresponding sulphamic acid, used in this modified process of the invention can be a member of any of the known series of diazotisable primary amines but preferably is a primary amine of the benzene or naphthalene series which optionally contain an arylazo group. The coupling component used in this modified process of the invention can be a member of any of the known series of coupling components but preferably it is a coupling component of the acylacetarylide, 5'-pyrazolone, phenol, naphthol or arylamine series.

, Those primary amines, or the corresponding sulphamic acid, and coupling components which contain at least one group of Formula I may themselves be obtained by treating the corresponding primary amine, or sulphamic acid, or coupling component containing at least one NHR group with (a) a 1:3:5-triazone or pyrimidine which carries at least one halogen atom and at least one group of Formula II, or (b) a z3z5-triazine or pyrimidine which carries at least 2 halogen atoms and then with a compound of Formula IV.

According to a further feature of the invention there is provided an alternative process for the manufacture of the new dyestuffs, as hereinbefore defined, which comprises reacting a dyestuff compound containing at least one NHR group, wherein R has the meaning stated above, with a 1:3:5-triazinne or pyrimidine which carries at least one halogen atom and at least one group of Forrnula H, as hereinbefore defined.

This alternative process of the invention may be conveniently brought about by adding a solution of the said dyestufl compound in water or in a water-soluble organic liquid or in a mixture of water and a water-soluble organic liquid to a solution or suspension of the said 1:3 :S-triazine or pyrimidine in water and/ or, a water-miscible organic liquid, stirring the mixture preferably at a temperature between 0 C. and C., adding sodium carbonate to maintain the pH of the mixture between 5 and 10, and filtering off the dyestuif which is precipitated. If necessary water and/ or sodium chloride can be added to ensure complete precipitation of all the dyestuif.

The 1:3:5-triazines or pyrimidines carrying at least one halogen atom and at least one group of Formula II may themselves be obtained by reacting a 1:3:5-triazine or pyrimidine carrying at least two halogen atoms with a compound of Formula IV.

According to a further feature of the invention there is provided a modified process for the manufacture of the new dyestuffs, as hereinbefore defined, wherein the 113:5- triazine or pyrimidine ring represented by Z carries one group of Formula II and one hydroxy group, alkoxy radical, aryloxy radical, mercapto or alkyl or aryl substituted rnercapto group or a substituted or unsubstituted amino group or a thiocyano or sulphonic acid group, which comprises reacting a new dyestuff containing a group of Formula II and a halogen atom attached to the 1:3 :S-triazine or pyrimidine ring, with a compound of the formula: WQ wherein W represents a hydrogen or a metal atom and Q represents a hydroxy group, alkoxy radical, aryloxy radical, mercapto or alkyl or aryl substituted mercapto group or a substituted or unsubstituted amino group or a thiocyano or sulphonic acid groups. This modified process of the invention may be conveniently brought about by stirring a mixture of the compound of the formula: WQ and the new dyestuif, as hereinbefore defined, in water, or in a water-miscible organic liquid or in a mixture of water and a water-miscible organic liquid, preferably at a temperature between 0 and C. adding sodium carbonate to maintain the pH of the mixture between 5 and 10, and filtering off the dyestutf which is precipitated. If necessary water and/or sodium chloride can be added to ensure complete precipitation of all the dyestuff.

As examples of compounds of the formula: WQ which may be used in this alternative process of the invention there may be mentioned methanol, phenol, ammonia, methylamine, diethylamine, aniline, orthanilic acid, metanilic acid, sulphanilic acid, sodium sulphite, potassium thiocyanate, methyl mercaptan, sodium hydroxide, phenyl mercaptan, aniline 3:5-disulphonic acid and anthranilic acid. I

If desired the new dyestuffs, as hereinbefore defined, can be isolated from the medium in which they have been formed and/or subsequently dried in the presence of a buffering agent. As examples of buifering agents which can be used for this purpose there may be mentioned buffering agents derived from phosphates such as sodium didydrogen phosphate and disodium hydrogen phosphate, citrates such as sodium citrate, borates and dialkylmetanilic acid such as sodium diethylmetanilate, which is preferably used in conjunction with sodium hydrogen sulphate.

One preferred class of the new dyestuffs of the invention are the water-soluble dyestuifs which contain at least one water-solubilising group, which is preferably a sulphonic acid group, and which contain one or two groups of the formula:

R N NR F r s N N R a i Halogen wherein R, R and R have the meanings stated above, and halogen represents a bromine atom or preferably a chlorine atom.

A second preferred class of the new dyestuffs of the invention are the water-soluble dyestuffs which contain at least one water-solubilising group, which is preferably a sulphonic acid group, and which contain one or two groups of the formula:

wherein R, R and R" have the meanings stated above.

A third preferred class of the new dyestuffs of the invention are the water-soluble dyestuffs which contain at least one Water-solubilising group, which is preferably a sulphonic acid group, and which contain one or two groups of the formula:

wherein R, R and R" have the meanings stated above and R is an allcyl radical, which is preferably a methyl radical.

A fifth preferred class of the new dyestuffs of the invention are the water-soluble dyestuffs which contain at least one water-solubilising group, Wl ich is preferably a sulphonic acid group, and which contain one or two groups of the formula:

wherein R, R and R" have the meanings stated above, Z represents a pyrimidine ring, halogen represents a chlorine or a bromine atom and n represents 1 or 2.

A sixth preferred class of the new dyestuiis of the invention are the water-soluble dyestuffs which contain at least one Water-solubilising group, which is preferably a sulphonic acid group, and which contain one or two groups of the formula:

wherein R, R and B" have the meanings stated above and X represents a hydrogen or a halogen atom. As examples of the halogen atoms represented by X there may be mentioned bromine and preferably chlorine.

The new dyestuffs, as hereinbefore defined, are valuable for colouring natural and artificial textile materials for example textile materials comprising cotton, viscose rayon, regenerated cellulose, wool, silk, cellulose acetate, polyarnides, polyacryionitrile, modified polyacrylonitrile, and aromatic polyester fibers. For this purpose the dyestuffs can be applied to the textile materials by dyeing, padding or printing using printing pastes containing the conventional thickening agents or oil-in-water emulsions or water-inil emulsions, whereby the textile mate-rials are coloured in bright shades possessing excellent fastness to light md to wet treatments such as washing.

The new dyestuffs which contain water-solubilising groups, for example sulphonic acid and carboxylic acid groups, which render them soluble in water are particularly valuable for colouring cellulose textile materials. For this purpose the dyest "Es are preferably applied to the cellulose textile material in conjunction with a treatment with aciding agent, for example sodium carhon-ate, sodium m licate, trisodium phosphate or sodium hydroxide, which may be applied to the cellulose textile material before, during or after the application of the dyestuff. Alternatively when dyed textile material is to be subsequently heated or steamed a substance such as sodium bicarbonate or sodium trichloroacetate, which on heating or steaming liberates an acid-binding agent can be used.

For example the cellulose textile material can be coloured by treating the cellulose textile material with an aqueous solution or suspension of the acid-binding agent and then immersing the sotreated cellulose textile material in a dyebatli comprising a solution of one or more of the new dyestuffs, as hercinbefore defined, at a temperature of between 0 and C., removing the dyed cellulose textile material from the dyebath and if desired subjecting the dyed cellulose textile material to a treatment in a hot aqueous solution or" soap.

if desired the cellulose textile material which has been treated with an aqueous solution or suspension of the acid-binding agent may be passed between rollers to remove excess aqueous solution or suspension of the acidbinding agent and/ or dried before being treated with the aqueous solution of the said dyestuiis.

Alternatively the aqueous solution of the dyestuil may be applied by padding to the cellulose textile material which has been treated with the acid-binding agent and the cellulose textile material then passed through rollers and subsequently subjected to the action of heat or steam. Alternatively the cellulose textile material can be padded with an aqueous solution of or more of the new dyestuffs, as hereinbefore defined, Which also contains an acid-binding agent, passing the so reated cellulose textile material through rollers, then if desired drying cellulose textile materifl at a suitable temperature, for example 79 (1., and then subjecting the cellulose textile material to the action of heat or steam. Alternatively the cellulose material can be dyed by immersing it in a dyebath comprising an aqueous solution of one or more of the said dyestuffs which also contains an acid-binding agent, at a suitable temperature for example between 0 and 10 (1., and thereafter removing the cellulose textile material from the dyebath, if desired subjecting it to a treatment in a hot aqueous solution of soap and finally drying the dyed cellulose textile material. Alternatively the aqueous solution of one or more of thesaid dyestuils can be applied to the cellulose textile material by a dyeing or a padding method and the coloured cellulose textile material subsequently immersed in an aqueous solution or suspension of the acid-binding agent, preferably at a temperature between C. and 100 C., or alternatively the coloured cellulose textile material may be padded With an aqueous solution or suspension of the acid-binding agent, the textile material dried and then subjected to the action of heat or steam. Alternatively the cellulose textile material can be dyed by immersing it in a dyebath comprising an aqueous solution of one or more of the said dyestuiis, preferably at a temperature between 20 and 100 C., and, after the textile material has absorbed some or all of the dyestuffs, adding an acid-binding agent and proceeding with the dyeing at the same or a difierent temperature.

The concentration of the acid-binding agent present in the aqueous solution of the dyestuffs is not critical but it is preferred to use between 6.1% and of the acidbinding agent based on the total weight of the aqueous solution. if desired the aqueous solution or suspension of the acid-binding agent may also contain further substances, for example electrolytes such as sodium chloride and sodium sulphate.

The aqueous solution of one or more of the said dyestuffs may also contain substances which are known to assist the application of dyestuffs to textile materials, for example sodium chloride, sodium sulphate, urea, dispersing agents, surface-active agents, sodium alginate or an emulsion of an organic liquid, for example trichloroethylene in water.

Alternatively the cellulose textile materials can be printed with a printing paste containing one or more of the new dyestuffs of the invention.

This may be conveniently brought about by applying a printing paste containing one or more of the said dyestuffs, to a cellulose textile material which has been impregnated with an acid-binding agent and thereafter subjecting the printed cellulose textile material to the action of heat or steam. Alternatively a printing paste con taining one or more of the said dyestuifs and containing an acid-binding agent can be applied to the cellulose textile material and the printed cellulose textile material subsequently subjected to the action of heat or steam. Alternatively a printing paste containing one or more of the said dyestuffs can be applied to the cellulose textile material which is subsequently immersed in a hot aqueous solution or suspension of the acid-binding agent or alternatively the printed textile material is impregnated with an aqueous solution or suspension of the acidbinding agent and subsequently subjected to the action of heat or steam.

After applying the printing paste to the cellulose textile material the printed textile material may, if desired be dried, for example at a temperature between 20 and 100 C. before the printed textile material is subjected to the action of heat or steam.

The cellulose textile material may be printed with the printing paste by any of the commonly known methods of applying printing pastes to textile materials, for example by means of roller printing, screen printing, block printing, spray printing or stencil printing. The printing pastes may also contain the commonly used adjuvants, for example urea, thickening agents, for example methyl cellulose, starch, locust bean gum, sodium alginate, waterin-oil emulsions, oil-in-water emulsions, surface-active agents, sodium m-nitrobenzene sulphonate, and organic liquids, for example ethanol.

At the conclusion of the dyeing and/or printing processes it is preferred to subject the so-colured cellulose textile materials to a spoaping treatment, which may be carried out by immersing the coloured cellulos etextile materials for a short time, for example minutes, in a hot aqueous solution of soap and/or detergent, and subi2 sequently rinsing the coloured cellulose textile material in water before drying it.

Those new dyestuffs which do not contain water-solubilising groups for example sulphonic acid, carboxylic acid, sulphonamide and acylsulphonamide groups are, in general, applied to textile materials in the form of an aqueous dispersion which may be obtained by gravel milling the dyestutf with water in the presence of a dispersing agent, for example the sodium salt of sulphonated naphthalene formaldehyde condensation products, sulphosuccinic acid esters, Turkey red oil, alkyl phenol/ethylene oxide condensation products, soap and similar surfaceactive materials with or without protective colloids such as dextrin, British gum and water-soluble proteins. If desired the aqueous paste of the dyestulf so obtained may be dried to form a re-dispersible powder which may be converted to a non-dusting powder by any of the processes known for forming non-dusting powders.

The new dyestuffs, as hereinbefore defined, can be applied to nitrogen-containing textile materials such as wool and polyamide textile materials, from a mildly alkaline, neutral or acid dyebath. The dyeing process can be carried out at a constant or substantially constant pH, that is to say the pH of the dyebath remains constant or substantially constant during the dyeing process, or if desired the pH of the dyebath can be altered at any stage of the dyeing process by the addition of acids or acid salts or alkalis or alkaline salts. For example dyeing may be started at a dyebath pH of about 3.5 to 5.5 and raised during the dyeing process to about 6.5 to 7.5 or higher if desired. The dyebath may also contain substances which are commonly used in the dyeing of nitrogen-containing textile materials. As examples of such substances there may be mentioned ammonium acetate, sodium sulphate, ethyl tartrate, non-ionic dispersing agents such as condensates of ethylene oxide with amines, fatty alcohols or phenols, surface-active cationic agents such as quaternary ammonium salts for example cetyl trimethylammonium bromide and cetyl pyridinium bromide and organic liquids such as n-butanol and benzyl alcohol.

Alternatively the new dyestuffs can be applied to textile materials, which are preferably cellulose textile materials, in conjunction with a treatment with a resin-forming composition and an acid-catalyst whereby the textile ma terial is simultaneously coloured and rendered resistant to creasing. This colouring process may be conveniently carried out by pading or printing the textile material with an aqueous solution containing (a) a new dyestuff, as hereinbefore defined (b) a resin-forming composition and (c) an acid-catalyst, optionally drying the treated textile material, and subsequently heating the textile material at a temperature above 0, preferably at a temperature between and C.

As examples of resin-forming compositions there may be mentioned epoxy resins, polyisocyanates, condensates of formaldehyde with cresols or with acrolein, and, in

particular mixtures comprising the methylol derivatives or lower alkyl ethers of methylol derivatives of monomeric or polymeric compounds containing a plurality of amino or mono substituted amino groups said compounds being known from the art or used in practice for the formation of resins by condensation with formaldehyde. Such compounds include, for example, monomeric nitrogen compounds such as urea, thiourea, substituted ureas and thioureas, dicyandiamide, dicyandiamidine, biguanides, amides, carbamatcs, allophanates and heterocyclic compounds such as aminotriazines, urons, ureins, ureides, imidazolidones, triazones and hydantoins, or mixtures of such compounds, and polymeric nitrogen compounds sucr as the polymeric amides made by the reaction of dibasic acids with diamines. The lower alkyl ethers of the methylol derivatives of these compounds include for example the methyl, ethyl, propyl and butyl ethers.

The quantity of the resin-forming composition which is present in the aqueous solution used in this colouring process usually amounts to between 3% and 30% by 13 weight of the aqueous solution and is preferably between and 20% by weight of the aqueous solution.

As examples of acid-catalysts there may be mentioned salts from weak bases and mineral acids such as Zinc 14 sodium chloride are then added and the dyestuil which is precipitated is filtered off and washed with 160 parts of a 25% aqueous solution of brine. The dyestuir" paste so obtained is mixed with 0.68 part of disodium hydrochloride, arnmonium sulphate, ammonium nitrate, am- 5 gen phosphate and 1.32 parts of potassium dihydrogen monium chloride and magnesium chloride and mineral phosphate and the resulting mixture is then dried. When acid salts of organic amines, which are preferably priapplied to cellulose textile materials in conjunction with mary or secondary organic amines which contain at least a treatment With an acid-binding agent the dyestull yields one allcyl chain carrying at least one hydroxy group. orange shades which possess excellent fastness to wet As specific examples of such primary or secondary amines N treatments. containing one or two hydroxyalkyl groups there may be Example 2 msntloned A solution of 9 parts of thioacetanilide in 30 parts of il-hydroxyethylamine, an 8% aqueous solution of sodium hydroxide is added N-methyl-N-(,B-hydroxyethyl)amine, with stirring to a solution of 14.3 parts of the trisodium N-ethyl-N-(,B-hydroxyethyl)amine, salt of l-(4:6'-dichloro-l:3':5-triazin-2-ylamino)-7- hydroxypropylamine, (2 sulphophenylazo)-8-naphthol-3:d-disulphonic acid fl-hydroxypropylamine, (which may be obtained as described in Example 4 of 5-, 'y or 6-hydroxy-n-butylamine, British specification No. 785,120) in 250 parts of water N :N-di(fl-hydroxyethyl)amine, and the mixture so obtained is stirred for 24 hours at N:N-di(,8-hydroxypropyl)amine, a temperature of 25 C. Any unreacted thioacetanilide is N-(fl-hydroxyethyl)-aniline or -benzylamine, then removed by passing carbon dioxide into the solution ,8:' -dihydroxypropylamine, and filtering off the solid which is precipitated. 120 parts N-methylglucamine (also known as N-methyl-N-pentaof potassium acetate are added to the filtra e so obtained hydroxy-n-hexylarnine), and the dyestutf which is precipitated is filtered oil, N-ethylglucamine, 25 Washed with 100 parts of ethanol, and dried. N-(p-hydroxyethyl)glucamine, When applied to cellulose textile materials in conjunc- N-methyl-N-(flz'y-dihydroxypropyl)amine and 2-aminotion with a treatment with an acid-binding agent the dyelz2z3-propanetriol. stuii yields bluish-red shades which possess excellent The invention is illustrated but not limited b the folfaslneess to i F lowing examples in which the parts and perceriiages are lhe i able gwes l examples of tbs nsw by Waight: dyestuifs or the uivention which are obtained when the Example 1 sodium salts of the azo compounds used 1n Examples 1 or 2 are replaced by equivalent amounts of the sodium A solution of 4.5 parts of thioacetamide in 30 parts of salts of the azo compounds which are obtained by conan 8% aqueous solution of sodium hydroxide is added (lensing cyanuric chloride with the sodium salts of the with stirring to a solution of 12.3 parts of the disodium aminoazo compounds listed in the second column of the salt of a 2-(4':6'-dichloro-1':3z5-triazin-2-ylamino)6- table and/or the thioacetamide used in Example 1 or (2" sulphophenylazo) 5 naphthol 7 sulphonic acid the thioacetanilide used in Example 2 are replaced by (which may be obtained as described in Examples 2 of equivalent amounts of the thio compounds listed in the British specification No. 785,120) in 350 parts of water, and the mixture so obtained is stirred for 24 hours at a temperature of 25 C. Acetic acid is then added until the pH of the mixture is between 6 and 7. parts of third column of the table. The fourth column of the table indicates the shades obtained when the dyestuffs are applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent.

She do obtained on Example Aminoazo compound Thio compound cellulose textile materials 3 l-amin0-7-(2sulphophenylazo)-8-napth0l-3zfi-disulphonic acid Thioacctamide luish-rcd.

Thiopr0pionamide. D0. dc Thiobenzamide... Do. Laminm'l-(phenylazo)-8-naphthol-3:G-disulphonic acid i0a0eta ide Z-amino-d-(Z-sulphophcnylazo)-5-napl1th0l-7-sulphonican 'lhloacetanilidc- Oran re. 3" 2-amin0-7-(2-sulphophcnylazo -8-naphtl1ol6-sulphonic acid. 9 1-(2:5-dichlor0-l-sulph0phenyl)-3-methyl-4-( -arnino-6-sulp Yellow.

pyrazolone. 1n do Thioacetarnide Do. 11 l-ST-Ohll l'0-5Sl1lph0phenyl -3111ethyl-d-(B"-amino-6"-sulphophenylazo)-5-pyrazo do Do.

0116. 2-amino-7(2-ol1lph04 mcthoxyplleriylazo)-8-naphthol (i-sulphonlcacid Thioacctanilidc Red. 2-methylamine-7-(2-sulpl1o-4'-methoxyphenylazo)-8-naphth0l-6-sulphonic acid. do Do. 2-amino-5-hydroxy-6z2-azonaphthalcne-Tz1:5-trisulphonic acid Orange. Z-meth ylamiue-hydroxy-G: Zhzonaphthalencfl 1 5 l7llSUlIJilOIllC acid 1 Do. 1:2-chrornium complex of Z-amino-d(Zcuboxyphenylazo)-5-ncphthol-7-sulphonic rown.

acid. 4-nitr0-4-(4-i -rncthylaminophenylazo)stilbene-Z :2-dlsulphonkic acid 1:2chromium complex of (i-emino-l:2-dihydroxy-6-nitro-2:l-azonaphthalcnc-3: t-

dlsulphonic acid. 2-(3-omino-lY-sulphophcnylazo) -1-naphthol-3 S-clisulphonic acid 2-arnino-6-(3-ainiuo-6-sulphophenylezo)-5-napl1tl2o1-7-sulphonic acid 2emino-6-[2\sulpl10-4(4-sulphophenylazo)phcnylaso]-dnaphtholJ-sulphonic -ulnino-5-l1ydroxy-6:2 azonaphtlmlone-7 :4 :8-trisulphonic acid 2-emino-5-hydroxy-S:2-azonaphthalcuc-7:5:7-trisulpllonic acid 1. .s. 2-( Y-amino-3-sulphophcnylarnino)-6-[2-sulpho--(p suipho phcnylnz0]-5-naphth0l-7-Sulphouic sci d. 2 amino-7-(3-nmino 6sulphophenylazo)-8-naphthol-fi sulphonic acid Z-amino-Shydrox 2-azonaphthelenc-6z4 :8-trisulphonie acid Q-emino-S-hvdmxy-Y Zamnsphthalenot; 1 5 'isulpllonic acid 1-amino-7 sulphophonylazo)-8-naphthol-3:tS-disulphonic acid 1-amin0-7-(2-sulpho 4-chlorophcny1azo)-8-naphthol-3 6- disulphon a 1-arnino-7- (2-sulpho-4-methoxyphcny1a 2o) 8-naphthel-3 G-dlsulplzonie eci l-arnino-Y 3-tunino- 6-sulphophenylazo) -8-napl1thol-3 fi-disulphonic acidl-emiud 2-sulph0phcnylezo)-8-naphtl1ol-4 ddisulphonlc acid l-arnino-S-hydroxy-T:Zamnephthaloned :6:1'trisulphonlc acid. Lamina-7 (4-sulpbophenylu2o)-8-nephthol-z6-disul ionic acid- 2-(2-ecetylamino-eminoplienylazo)naphthalenc-4: disulphonie acid 2-(2-methyl-4emincphenylazo)nephthalenc-5:7-disulphonic acid 2-[2-mcthyl-4'- (4"-amino-2"-mcthylphcnylazo) phenylaz01naphthalene-4 :8-

disulphonic acid.

Thioacctamide Thioacetanilide Reddish-yellow. B is oh Eeddish-orangc.

Rcddishorange. Red.

Do. Bluish-red.

Do. Rubine. Bluish-red. Re Rubine. Bluish-red. Re ddish-yellow.

o. Brownish-orangc.

Shade obtained on Example Aminoazo compound Thio compound cellulose textile matcrials 1- (2-sulph0phenyl)-3mcthyl-4- (3 -amino-6-sulph0phenylazo)-5-pyrazol0ne Yellow 1-(3-arniu0-6sulph0phcnylazo)-2-naphthol-6-sulphonie acid 1-(3-amino-6-sulphophcnylazo)-2-naphthol-6 :B-disulphonic acid. 2-(3-amiuo-6-sulphophcnylazo)-1-naphthol-3-sulphonic acid... 2-(3-amin0-6-sulphophcuylaz0)-l B-dihydroxynaphthalene-Bz fi-disulphonic acid.-... 1-(3-amiuo-6sulphopl1cnylazo)-2-amino-8-naphthol-G-sulphonic acid 1-acetylamino-7-(3-amino-6-sulphophenylazo)-8-naphthol-3 zfi-disulphonic acid 1-acctylamino-7-(3-amino-6-sulpliophenylazo)-8-naphthol-4 :G-disulphonic acid l-bcnzoylamin-7-(3-amino-6-sulphophcnylazo)-S-naphthol-3 zfi disulphonic acid. 2-propionylamino-6-(3-arnino-6-sulphophcnylazo)-5-naphthoI-7-sulphonic acid 2-bcnzoylamino-G-(3-amino-6-sulphophcnylazo)-5-naph th ol-7-sulphonic acid Thioiacetanilide 4-ohlorothiopropionanilidc Thioacct-p-toluidide- Thioacet-m-toluidide.- Thi0acetamide..

0 range. Do.

Do. Bluish-rcd. Red.

Do. Ycllcwish-red.

1-(4-auiino-2-sulphophonylazo)2-naphthol-8-sulphonic acid d Rod. 2-acetylamino-6(4-amino-2-sulphophenylaz0)-S-naphthol-7-sulph0nic acid -.do. Yellowish-rcd. 2-acetylemin0-7-(4-amino-2-sulphophenylazo)-8-naphthol-6-sulphonic acid -do. Red. l-(4-amin0 2-su1phophcnylazo)-2-amin0-8-naphthol-fi-sulphonic acid ..do. llluish-rcd. l-acetylainino-7-(-a1nino-2-sulphophcnylazo)-8-naphthol-3:(i-disulphonic acid. N-cthylthiobcnzamidc Violet. 1-beuzoylamino-7-(4'-amino-2-sulr-l1ophenylazo)-8-naphthol-4:o-disulphonic acid Phcnyll'liioacetamide. Bordeaw. 1-(3an1inopl1eny1)-3-mctliyl 4-(4 5-disulphophcnylazo)-5-pyrazolone 2-mcthylthiobenzamid 'ellow. 1-(3-au1inobcnzoylamino)-7-(2-sulphophenylazo) '8-naphth0l-3:ti-disulphonic acid.-. Thioacet-p-toluidc- Red. l-(ai-amiuostclllphonaphth-lylazo)-4-(8-sulphcnaphthl-ylazo)-naphthaleue sul- Thioaceta1nide.. Reddish-brown.

ionic aci 1 -lnil102- (4-aminophenylazo) -7- (4-sulpl1ophenylazo)-8-naphth 01-3 ddisulphonic Thioacctanilide. Green.

acid. 1-(4-arnin benzoylaniino)-7-(2"-sulphophenylazo a8-naphthol-3:(i-disulphdnic acid- Red. 1-ain1ino-7-(2-sulphoplicny1azo) -8-naph dial-3 :6- disulplionic acid. Bluibh-rcd. 0.. o. 0.. Thio-dnaphthamidc Do. 2-amino-d[2-methoxy-5-methyl-4-(2:5-disulphophenylazo)-phenylazo]5-naph- Thloacetanilidc. Bluish-violet.

thol-l 7-disulphonlc acid. l-(3 rmtinophenyl)-3-earboxy-4-(1:5-disulphonaphth 2-y1azo)-5-pyrazolcne Rcddish-yellow. l-arnlno-7-(2-hydroxy-5-sulphophcnylazo)-8naphth0l-3:G-dlsulphonic acid Bl e, l-amino-7-(2"hydroxy-3-nltr0-5-sulphophenylazo)-8-naphthol-3:6-disulphonic ac1d Do. lz2-cobalt complex of 1-(3-amino-4-sulphophcnyl)-3-metliyli-(2-carboxyphenyl- Yellow az0)5-pyrazolone. 2-amino-6-(2-hydroxy-5-sulphophenylazo)-5-naphth0l-l :7-disulphon1c acid Violet. Z-N -methy1amino-6-(2'-sulpho-4'-methoxyphcnylazo)-5-naphtho1-7-sulphonic acid-- Scarlet 1 -amin0-7- [4 (o-sulphophenylazo) -2 -Inethoxy-5-methylphcnylazol-dnaphth01-3 :6 lue.

disulphonic acid. g5 2-(4-am1no-2-methylphenylazo)naphthalene-4 :8-d1sulph0n1c acid 1. Yellgw. 6 .(10 e (L 77 2-arnino-6-(2-sulpho-4-methoxyphenylazc)-5naphth0l-7-Sulph0nil3 acid.. Thioacetanilide Scarlet. 78 1-amino-7-(2-su1 hopheny1azo)-8-mphthol-3zo-disulphcnic acid p-Chlorothlo-acctanilide Bluish-rcd.

Example 79 A mixture of 6 parts of the dyestutl of Example 69, 3 parts of copper sulphate pentahydrate and 130 parts of water is stirred for 4 hours at a temperature between and C., the pH of the mixture being maintained between 6.0 and 6.5 by the gradual addition of an aque- 'ous solution of sodium carbonate. An aqueous solution of sodium carbonate is then added until the pH of the mixture is 7 and the mixture is filtered. 40 parts of sodium chloride are added to the filtrate and the dyestuif which is precipitated is then fi ltered oif. The solid so obtained is mixed with 0.99 part of disodiurn hydrogen phosphate and 2.01 parts of potassium dihydrogen phosphate and the mixture is then dried.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the copper-containing dyestuif so obtained yields violet shades which possess excellent fastness to wet treatments.

In place of the 6 parts of the dyestufi of Example 69 used in the above example there are used equivalent :amounts of the dyestuffs of Examples 70 and 72 whereby copper-containing dyestufls are obtained which colour cellelose textile materials in violet and rubine shades respectively.

Example 80 tone and dried. When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestuft yields blue shades which possess excellent fastness to wet treatments.

Example 8] A solution of 4.53 parts of thioacetanilide in 10 parts of a 10% aqueous solution of sodium hydroxide is added with stirring to a solution of 15.66 parts of the trisodium salt of 1-arnino-4-[4'-(4":6"-dichloro-1:3:5"-triazin- 2" ylamino)anilino]anthraquinone 2:3:5 trisulphonic acid in 500 parts of Water and the resulting mixture is stirred for 18 hours at 25 C. Any unreacted thioacetanillide is then removed by passing carbon dioxide into the solution and filtering ed the precipitated solid. 50 parts of sodium chloride are then added and the dyestuit which is precipitated is filtered off and dried.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestuff yields b'lue shades which have excellent fastness to wet treatments.

The following table gives further examples of the new dyestulfs of the invention which are obtained when the sodium salts of the anthr-aqui-none compounds used in Examples or 81 are replaced by equivalent amounts of the sodium salts of the anthraquinone compounds which are themselves obtained by condensing the aminoanthraquinones listed in the second column of the table with the heterocyclic compounds listed in the third column of the table, and/ or the thioacetamide used in Example 80 or the thioacetanilide used in Example 81 are replaced by equivalent amounts of the thio compounds listed in the fourth column of the table. The fifth column of the table indicates the shades obtained when the dyestuffs are applied to cellulose textile materials in conjunction With a treatment with an acid-binding agent.

Example Aminoanthraquinone Heterocyelie compound Thio compound Shade 82 l-arfiinoi-(i liaminoanilino) anthraquinone-2:4-disul- 5-cyano-2:4z6-trichloropyrimidine- Thioacetauilide Blue.

p onie aci 83 1-arnino4-(4-aminoanillno) anthraquinone-2:3-5-trido do Do.

sulphonic acid.

1 d Thioacetamide Do. rln d-ohlorothioacetanilide- Do. Cyanuric chloride 87 do 2:4:5:G-tetrahelem-pyrimidine... D 88 Mixture of l-amind-[4-(4-aminophenylazo)-anilino] Oyanuric chloride anthraquinone-2:2:5 and -2:2:8-trisulpho1n'c acids. 89 do Cyanuric bromide 9 n 5-cyano-2 :4: 6-trichloropyrimidine 91 Mixture of 1-amino-4-[4-{fl-(4-aminopheuy1)vinyl}- do aniline] anthra quinone-2 2 :3 z5- and -2 2 :3 :8-tetrasulphonic acids. 92 do Cyanuric chloride i-methylthioacet- Do.

an e. 93 Mixture of 1-amin0-4-[4-{fi.-(4-amin0phenyl)vinyl1- do Thioaeetanilide D0.

amhnOIanthraquinQne-Z :2 :3 :5- and -2: 2 :3 ;8-tetrasulphonic acids. 94 d0. 2:4:5:fi-tetrachloro-pyrimidhle do D0.

Example 95 A solution of 9.1 parts of the disodium salt of l-amino- 8-naphthol-3:6-disulphonic acid in 100 parts of water is added, during 30 minutes, to a suspension of 4.65 parts of cyanuric chloride in a mixture of 30 parts of acetone, 50 parts of ice and 50 parts of water. The resulting mixture is stirred for 1 hour at a temperature between 0 and 5 C. and a 10% aqueous solution of sodium carbonate is then added until the pH of the mixture is 7. A solution of 3.78 parts of thioacetanilide in 10 parts of a 10% aqueous solution of sodium hydroxide is then added and sodium carbonate is added until the pH of the mixture is between 8 and 9. The mixture is stirred for 1 hour at 35 C. then cooled to 0 C. and an aqueous solution of diazotised orthanilic acid (obtained by diazotising 4.1 parts of orthanilic acid in the normal manner) and 10 parts of sodium carbonate are added. The mixture is stirred for 2 hours at 0 C., 40 parts of sodium chloride are added and the precipitated dyestuff is filtered off and dried. The dyestuff so obtained is identical to the dyestutf of Example 2.

Example 96 19.7 parts of copper phthalocyanine-3-sulphon-N-(3'- aminophenyl)amide sulphonamide sulphonic acid (which may be obtained as described below) are suspended in 400 parts of water and a 2 N aqueous solution of sodium hydroxide is added until a clear solution is obtained and the pH of the solution is 7. The solution is cooled to between 0 and 5 C. and a solution of 3.88 parts of cyanuric chloride in parts of acetone is then added. The mixture is stirred for minutes at a temperature between 0 and 5 C. whilst maintaining the pH of the mixture between 6.5 and 7 by the addition of a 2 N aqueous solution of sodium carbonate. A solution of 4.5 parts of thioacetanilide in 30 parts of a 2 N aqueous solution of sodium hydroxide is then added and the mixture is slowly heated to a temperature of 20 C. and maintained at this temperature for 16 hours. The pH of the mixture is then adjusted to between 6.0 and 7.0 by the addition of a 2 N aqueous solution of acetic acid. 150 parts of sodium chloride are then added and the precipitated dyestuff is filtered oif and dried.

When applied to cellulose textile materials by a printing process the dyestutf yields bright greenish-blue prints possessing excellent fastness to wet treatments.

The copper phthalocyanine-3-sulphon-N-(3-aminophenyl)-amide sulphonamide sulphonic acid used in the above example may be obtained as follows:

115.2 parts of copper phthalocyanine are slowly added with stirring to 540 parts of chlorosulphonic acid and the mixture is then stirred for 3 hours at a temperature between 140 C. to 145 C. The mixture is cooled to 80 C., 100 parts of thionyl chloride are added and the mixture is then stirred for 2 hours at a temperature of C. The mixture is cooled to 20 C., poured on to ice and the precipitated phthalocyanine sulphonchloride is filtered off and washed with 1000 parts of a 1% aqueous solution of hydrochloric acid which has been cooled to 0 C.

The solid sulphonchloride so obtained is stirred with 1000 parts of water and 600 parts of ice and 30 parts of m-aminoacetanilide are then added. The pH of the resultant mixture is adjusted to 8 by the addition of a 2 N aqueous solution of ammonium hydroxide and the temperature of the mixture is then raised to 50 C. during 1 hour, the pH of the mixture being maintained at 8 by further additions of a 2 N aqueous solution of ammonium hydroxide. The mixture is then stirred at a temperature of 50 C. until no further additions of ammonium hydroxide solution are required to maintain the H at 8. 500 parts of a concentrated aqueous solution of hydrochloric acid are then added and the mixture is stirred for 4 hours at a temperature of C. The mixture is then cooled to 20 C. and the precipitated solid is filtered 01f, washed with a 1% aqueous solution of hydrochloric acid and dried.

Example 97 19.7 parts of copper phthalocyanine-3-sulphon-N-(3'- arninophenyDamide sulphonamide sulphonic acid (which may be obtained as described in Example 96) are suspended in 400 parts of water and a 2 N aqueous solution of sodium hydroxide is added until a clear solution is obtained and the pH of the solution is 7. The solution is cooled to between 0 and 5 C. and a solution of 3.88 parts of cyanuric chloride in 20 parts of acetone is then added. The mixture is stirred for 30 minutes at a temperature between 0 and 5 C. whilst maintaining the pH of the mixture between 6.5 and 7 by the addition of a 2 N aqueous solution of sodium carbonate. A solution of 9 parts of thioacetanilide in 30 parts of a 2 N aqueous solution of sodium hydroxide is then added and the mixture is slowly heated to a temperature of 20 C. and maintained at this temperature for 16 hours. Any unreacted thioacetanilide is then removed by passing carbon dioxide into the solution and filtering oh" the precipitated solid. parts of sodium chloride are then added and the precipitated dyestufi is filtered off and dried.

When applied to cellulose textile materials by a printing process the dyestufr yields bright greenish-blue prints possessing excellent fastness to wet treatments.

The following table gives further examples of the new dyestuiis of the invention which are obtained when the 19.7 parts of the copper phthalocyanine derivative used in Example 96 or 97 are replaced by equivalent amounts of the copper phthalocyanine derivatives listed in the second column of the table, and/or the 3.88 parts of cyanuric chloride used in Example 96 or 97 are replaced by equivalent amounts of the heterocyclic compounds listed in the third column of the table, and/ or the 4.5 parts of thioacetamide used in Example 96 or the 9 parts of thioacetanilide used in Example 97 are replaced by equivalent amounts of the thio compounds listed in the fourth column of the table. The fifth column of the table indicates the shades obtained when the dyestuffs are applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent.

Example Copper phthalocyanine derivative Hcterocyclic compound Thio compound Shade 98 Copper phthalocyanine-3-sulphon-N-(4-amin0phenyl)- -cyan0-2:4:6-trichloropyrimidine. Thioacetamide Greemsh-blue.

amide sulphonamide sulphonic acid.

99 do 2:415:6-tetrachloropyrimidme do Do.

100 do 5-methy1-2:4:fi-trichloropyrimidine Thioacetamlide- Do.

101 Copper phthalocyanine-4-su1phon-N-(3-aminopheny1)- Cyauun'c chloride do D0.

amide sulphonamide sulphonic acid.

102 d0 do Thioace nid Do.

103 Copper phthalocyanine-4-sulphon-N-(4-aminophenyl)- do S-methylthroacetam- Do. amide sulphonamide sulphonic acid. v lrde.

104 do Cyanuric br0m1de Thropropronam1de- Do.

105 Copper phthalocyanine-l-sulphon-N-(3-amino-4-methyl- Cyanuric chloride Thloacetanlhde Do.

phenyDamide sulphonamide sulphonic acid. 7 V

106 Copper phthalocyanine-4-su1phon-N -(3-amino-4-chl0rodo Th10benzam1de Do.

phenyl) amide sulphonamide sulphonic acid.

107 Copper phtha1ocyanine-4 suphon-N-(4-amino-3'-sulphodo Thwacetamidc Do.

phenyl) amide suphonic acid.

The copper phthalocyanine 3 sulphon N-(4'-aminophenyl)-amide sulphonamide sulphonic acid used in the above examples may be obtained by the method described in Example 96 for the preparation of the isomeric compound except that the 30 parts of m-aminoacetanilide are replaced by 30 parts of p-aminoacetanilide.

The copper phthalocyanine 4-sulphon-N-[3'-aminophenyl or 4-aminophenyl or 3'-amino-4'-methylphenyl or 3'-amino-4'-chlorophenyl] amide sulphonamide sulphonic acid used in the above examples may be obtained as follows:

196.8 parts of the tetrasodium salt of copper phthalo cyanine tetra-4-sulphonic acid are slowly added with stirring to 970 parts of chlorosulphonic acid and the mixture is then stirred for 3 hours at a temperature between 115 C. and 120 C. The mixture is cooled to a temperature of 80 C., 100 parts of thionyl chloride are added and the mixture is stirred for 2 hours at a temperature between 115 and 120 C. The mixture is then cooled to C., poured on to ice, and the precipitated phthalocyanine sulphonchloride is filtered oil, and washed with 1000 parts of a 10% aqueous solution of hydrochloric acid which has been cooled to 0 C.

The sulphonchloride so obtained is stirred with 1000 parts of water and 600 parts of ice and 30 parts of maminoacetanilide or 30 parts of p-aminoacetanilide or 32.8 parts of 3-amino-6-methylacetanilide or 36.9 parts of 3-amino-6-chloroacetanilide respectively are then added. The pH of the resulting mixture is adjusted to 8 by the addition of a 2 N aqueous solution of ammonium hydroxide and the temperature of the mixture ,is then raised to 50 C. during 1 hour, the pH of the mixture being maintained at 8 by further additions of a 2 N aqueous solution of sodium hydroxide. The mixture is then stirred at a temperature of 50 C. until no further additions of the ammonium hydroxide solution are required to maintain the pH at 8. 500 parts of a concentrated aqueous solution of hydrochloric acid are then added and the mixture is stirred for 4 hours at a temperature of 90 C. The mixture is cooled to 20 C. and the precipitated solid is filtered otT, washed with a 1% aqueous solution of hydrochloric acid and dried.

Example 108 A solution of 3.78 parts of thioacetamide in parts of an N aqueous solution of sodium hydroxide is added with stirring to a solution of 15.5 parts of the disodium ride are then added and the precipitated dyestufl is filtered oif and dried.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestufi yields yellow shades possessing excellent fastness to Wet treatments.

Example 109 7.73 parts of the trisodium salt of 2-[8-hydroxy-7'- (2"-sulphophenylazo 3' 6'-disulphonaphth -l-ylamino] 4-anilino-6-chloro-1:3:S-triazine and 3.02 parts of thioacetamide are dissolved in 250 parts of water containing 8 parts of a 10% aqueous solution of sodium hydroxide. The solution is then stirred at 50 C. for 12 hours. 37 parts of sodium chloride are then added, the solution is cooled to 30 C. and the dyestuif which separates out is filtered off, washed with acetone and dried.

When the dyestufi is applied to cotton in conjunction with a treatment with an acid-binding agent bluish-red shades are obtained which have excellent fastness to Washing.

Example 110 6.43 parts of the disodium salt of 2-[5'-hydroxy-6'- (4"-methoxy-2"-sulphophenylazo)- 7'-sulphonaphth-1'-ylmethyl-amino1-4 methoxy 6-chloro-1:3:5-triazine and 3.02 parts of thioacetanilide are dissolved in 250 parts of water containing 8 parts of a 10% aqueous solution of sodium hydroxide. The solution is then stirred at 50 C. for 12 hours. 12.5 parts of sodium chloride are added, the solution is cooled to 20 C. and the dyestuff which separates out is filtered oif, washed with acetone and dried.

When applied to cellulose textile materials in the presence of an acid-binding agent the dyestufif yields bright scarlet shades which have very good fastness to Washing.

The following table gives further examples of new dyestufifs of the invention which are obtained when the 7.73 parts of the trisodium salt of the azo compound used in Example 109 are replaced by equivalent amounts of the sodium salts of the azo compounds which are obtained by condensing the aminoazo compound listed in the second column of the table with the heterocyclic compound listed in the third column of the table. The fourth column of the table indicates the shades obtained when the dyestuffs are applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent.

Example Amiuoazo compound Heterocycllc compound Shade 111 1-aminO-7-[4'-(phenylazo)-2-meth0xy-5-methyl-phenyl- 2-phenoxy-4:6-dichloro-1z3z5-triazine Blue.

azo]-8-naphthol-3 :2 16-trisulphonic acid. 112 1-(3-aminophenyl)-3-carboxy-4-(1:5-disulph0naphth- 2-(3-sulphophenylamino)-4:G-dibromo-l:3:5-triazine Yellow.

2 ylazo) 5-pyrazolone. 113 1 -benzoylamino -7 (2J- aminophenylazo)- 8 naphthol 2-(3 :5-disulphophenylamino)-4:6-dicl1loro-113:5-triazine- Red.

3:6:6-trisu.lph0nic acid. 114 2-(4lagnino -2 nethylphenylazo)-naphthalene-4:8-di- 2 methoxy-4:6-dichloro-l:3z5-triazine Yellow.

S11 p 01110 2101 115 1-(2:5-dichloro4sulphophonyl)3-methyl-4-(3' ami- 2-amino-416-dichloro-1:3:5-triazine Do.

n-6sulphophenylazo)-5-pyrazolone. 116 2-methylamino-5-hydroxy-fiz2-azonaphthalcne-7:1:5- 2-methylamin0-4:G-dichloro-lz3z5-triazine Orange.

trisulphonie acid. 117 i-gitro-ii-(4-Nhmethylaminophenylazo)stilbene-2:2 2-dimethylamino-4:6-dichloro-113:5-triazine Reddish-yellow.

isulp onic aci 1aginoe-hdydroxyflz2-azonaphthalene3:6:1-trisul- 2-(4'-su1phoanilino)4:6-dichloro-1:3:5-triazine Rubine.

p onic aci 1-(Zi amino g-sulphophenylazo)-2-naphthol-6:8-disul- 2-methyl-4:6-dichlorod23z5-triazine Orange.

p 101110 aci 1 amino 2 (4 aminophenylazo) 7 (4 sulpho 2-methlthio-4:6-dich1oro-1:3:5triazine Green.

phenylazo)-8-naphthol-3 :fi-disulphonic acid. Z-aInLIno-G-(2-sulphophenylazo)-5-naphthol-7-sulphonic Z-phenylthio-al:fi-dlchlorod :315-triazine Orange.

9.01 1-amino-7-(a sulphophenylazo) -8-naphthol-42ddisul- 2-phenyl-4:6-dicl1loro-l:3:5-triazine Red.

phonic 2.0K 123 do -cyano-2z4rfi-trichloropyrimidine Do. 124 2-methylamino-S-hydroxy-G:2-azonaphthalenc-7 :1 :5- o. Orange.

trisulphonic acid. 125 do 2:4:5:G-tetrachloropyrimidine Do. 126 1-amino-8-hydroxy-7:2-azonaphthalene-3:6:1-trisul- 5-cyan0-2-methyl-4:G-dichloropyrimid D0.

phonic acid. 127 aarrd'ino e-(2' sulphophenylazo)-5-naphtho1-7sulphonic 5-cyano-2:4:6-tr1ch1oropyr1midinc Do.

Example 128 6.13 parts of the dyestuff 'of Example 75 and 2.14 parts of the sodium salt of aniline-S-sulphonic acid are dissolved in 250 parts of water, and the solution is then stirred at 40 C. for 8 hours. 37.5 parts of sodium chloride are added and the solution is cooled to C. The precipitated dyestuif is then filtered off, washed with acetone and dried.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestuff yields yellow shades which have good fastness to washing.

The following table gives further examples of new dyestuffs of the invention which are obtained when the 6.13 parts of the dyestuff of Example 75 which are used in Example 127 are replaced by equivalent amounts of the dyestuffs listed in the second column of the table and/ or the 2.14 parts of the sodium salt of aniline-3-sulphonic acid used in Example 127 are replaced by equivalent amounts of the sodium salt of the compound listed in the third column of the table. The fourth column of the table indicates the shades obtained when the dyestuffs are applied to cellulose in conjunction with a treatment with an acid-binding agent.

Example 135 100 parts of bleached cotton fabric are padded through an aqueous solution containing 1% of the dyestuff of Example 1, 1% of sodium bicarbonate and 0.2% of an alkylated phenol/ ethylene oxide condensate, at a temperature of 18 C., and the cotton fabric is then squeezed between rollers until its weight is 200 parts. The cotton fabric is dried at 70 C. and is then exposed to steam at a temperature of 102 C. for 1 minute. The coloured cotton fabric is then rinsed in water, immersed for 15 minutes in a 0.2% aqueous solution of soap, rinsed again in water and finally dried.

The cotton fabric is thereby coloured a bright orange shade possessing excellent fastness to washing.

In place of the 1% of the dyestuif of Example 1 used in the above example there is used 1% of the dyestulf of Example 2 whereby the cotton fabric is coloured in bright bluish-red shades which possess excellent fastness to washing.

Example 136 100 parts of bleached cotton yarn are immersed in a dyebath comprising 2 parts of the dyestuff of Example 2 and parts of sodium chloride dissolved in. 3000 parts of water and dyeing is carried out for 30 minutes at a temperature of 20 C. 5 parts of trisodium phosphate are then added and dyeing is continued for 60 minutes at 20 C. The dyed cotton ymn is then removed from the dyebath, rinsed in Water, immersed for 5 minutes in a 0.2% aqueous solution of a synthetic detergent at a temperature of C., rinsed again in water and finally dried. The cotton yarn is dyed a bright bluish-red shade which is fast to washing.

Example 137 100 parts of bleached cotton fabric are padded through an aqueous solution containing 0.2% of the dyestuff of Example 78 and 2% of sodium carbonate and the cotton fabric is then passed between rollers until its weight is 200 parts. The cotton fabric is then rolled up and stored for 4 hours at a temperature of 20 C. The cotton fabric is then rinsed in Water, immersed for 5 minutes in a 0.2% aqueous solution of a synthetic detergent at a temperature of 100 C., rinsed again in water and dried. The cotton fabric is coloured a bright bluish-red shade possessing excellent fastness to washing.

Example 138 100 parts of woollen cloth are immersed in a dyebath comprising a solution of 1.5 parts of the dycstuff of Ex ample 77, 3.0 parts of ammonium acetate, 0.5 part of cetyltrimethylammonium bromide and 1.0 part of a condensate of ethylene oxide with a fatty alcohol in 5000 parts of water, and dyeing is carried out for 1 hour at a temperature of 100 C. The dyed woollen cloth is then removed from the dyebath, rinsed in Water and dried. The woollen cloth is dyed a scarlet shade possessing excellent fastness to washing.

23 Example 139 A print paste comprising:

Parts The dyestufl? of Example 12 3 Urea 10 Water 50.8 Sodium bicarbonate 1.2 4% aqueous solution of sodium alginate 35 is applied to unmercerised cotton cloth by machine printing. The printed cotton cloth is dried at a temperature of 70 C. and is then steamed for 6 minutes at a temperature of 100 C. The printed cotton cloth is then rinsed in water, immersed for 10 minutes in a 0.3% aqueous solution of a synthetic detergent at a temperature of 100? C., rinsed again in water and finally dried.

The cotton cloth is thereby printed a red shade which possesses excellent fastness to wet treatments.

In place of the unmercerised cotton cloth used in the above example there may be used mercerised sateen cloth or viscose rayon cloth when red prints are also obtained which possess excellent fastness to wet treatments.

Example 140 100 parts of mercerised bleached cotton material are padded through an aqueous solution containing 2.0% of the dyestufi of Example 3, 10% of dimethylolglyoxal monourein, 1.0% of N:N-di(fi-hydroxyethyDan-nine hydrochloride, 1.0% of methylol stearamide and 0.5% of sodium triisopropylnaphthalene sulphonate, and the cotton material is then squeezed between rollers until its weight is 200 parts. The cotton material is dried at a temperature of 70 C. and is then baked for 3 minutes at a temperature of 155 C. The cotton material is then rinsed in water, immersed for minutes in a boiling aqueous solution containing 0.5% of sodium carbonate and 0.1% of a mixture of an alkylated phenol/ ethylene oxide condensate and a sulphated fatty alcohol, rinsed again in water and finally dried.

The cotton material is coloured a bright bluish-red shade which possesses excellent fastness to light and to wet treatments and the cotton material is resistant to creasing.

Example 141 100 parts of a bleached mercerised cotton poplin are padded through an aqueous solution containing 1.0% of the dyestuff of Example 15, of trimethylolmelamine, 1.5% of N-(fi-hydroxyethyl) N (/3 hydroxy-n-butyD- amine hydrochloride, 1.0% of methylolstearamide, 0.3%

of sodium triisopropylnaphthalene sulphonate and 0.3% of sodium chloride and the cotton poplin is then squeezed between rollers until its weight is 200 parts. The cotton poplin is dried at a temperature. of C. and is then baked for 3 minutes at a temperature of C. The cotton poplin is then rinsed in water, immersed for 5 minutes in a boiling aqueous solution containing 0.5% of sodium carbonate and 0.1% of a mixture of an alkylated phenol/ethylene oxide condensate and a sulphated fatty alcohol, rinsed again in water and finally dried.

The cotton poplin is coloured a bright orange shade which possesses excellent fastness to light and to wet treatments and the cotton poplin is resistant to creasing.

What We claim is:

Dyestuffs having the formula:

D is a chromophoric dyestufis radical selected from the class consisting of azo, nitro, anthraquinone, and

phthalocyanine chromophoric dyestuifs radicals; R

is a radical selected from the class consisting of hydrogen and lower alkyl; Z represents a heterocyclic ring selected from the class consisting of 1:3:5-tria zine and pyrimidine rings, attached to the nitrogen atom through a carbon atom of said ring, and carry ing at least one group of the formula:

in which R and R" stand for a member selected from the class consisting of hydrogen, lower alkyl,

monocyclic aryl, monocyclic aryl lower alkyl, and

dicyclic aryl; and any further substituents attached to said heterocyclic ring are selected from the class consisting of chlorine, bromine, methyl mercapto, phenylmercapto, methyl, phenyl, methoxy, phenoxy, amino, methylamino, dimethylamino, anilino, sulfonanilino, disulfoanilino, carboxyanilino, and cyano radicals.

References Cited in the file of this patent UNITED STATES PATENTS 1,667,312 Fritzsche et al Apr. 24, 1928 1,886,480 Haller et al. Nov. 8, 1932 2,332,047 Bock et al. Oct. 19, 1943 2,339,739 Blackshaw et al. Jan. 18, 1944 2,350,188 Pinkney May 30, 1944 2,728,761 Wallace et a1 Dec. 27, 1955 2,795,576 Fasciati June 11, 1957 

